EP1563012B1 - Trisazo dyes for inks for ink jet printing - Google Patents

Trisazo dyes for inks for ink jet printing Download PDF

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Publication number
EP1563012B1
EP1563012B1 EP03811422A EP03811422A EP1563012B1 EP 1563012 B1 EP1563012 B1 EP 1563012B1 EP 03811422 A EP03811422 A EP 03811422A EP 03811422 A EP03811422 A EP 03811422A EP 1563012 B1 EP1563012 B1 EP 1563012B1
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EP
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Prior art keywords
alkoxy
sulpho
carrying
carboxy
optionally substituted
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EP03811422A
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German (de)
English (en)
French (fr)
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EP1563012A1 (en
Inventor
David Phillip Devonald
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Fujifilm Imaging Colorants Ltd
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Fujifilm Imaging Colorants Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/34—Hot-melt inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/36—Trisazo dyes of the type
    • C09B35/362—D is benzene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/24—Disazo or polyazo compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes

Definitions

  • IJP ink jet printing
  • IJP Inks used in IJP.
  • IJP Inks
  • they desirably provide sharp, non-feathered images having good waterfastness, light-fastness and optical density.
  • the inks are often required to dry quickly when applied to a substrate to prevent smudging, but they should not form a crust over the tip of ink jet nozzles because this will stop the printer from working.
  • the inks should also be stable to storage over time without decomposing or forming a precipitate which could block the fine nozzles.
  • JP 58-174459 describes certain dis-azo dyes comprising once-coupled 1,8-dihydroxynaphthalene and their use in ink jet printing.
  • JP 57-36693 and US 4,395,288 describe certain tetra-azo dyes comprising 1,8-dihydroxynaphthalene and their use in ink jet printing.
  • GB 809279 published in 1959, describes the synthesis of copper complexes of certain tris-azo dyes comprising once-coupled 1,8-dihydroxynaphthalene and a 3,3'-dimethoxy-1,1'-diphenyl linker. These dyes are used for the conventional dyeing of cotton.
  • DE 268 488 , DE 87 973 , DE894 423 and GB 1 569 259 also disclose tris-azo dyes while WO01/62854 discloses the use of chelated tris-azo dyes in ink-jet printing.
  • the tris-azo dyes of the present invention have exceptional properties when used as ink jet inks, producing prints of high optical density (OD) of a neutral black with excellent light and ozone-fastness and high operability.
  • a process for printing an image on a substrate comprising applying thereto a composition comprising a liquid medium and a tris-azo compound of Formula (1) or salt thereof: wherein:
  • the composition is applied to the substrate by means of an ink jet printer.
  • the ink jet printer preferably applies the composition to the substrate in the form of droplets which are ejected through a small orifice onto the substrate.
  • Preferred ink jet printers are piezoelectric ink jet printers and thermal ink jet printers.
  • thermal ink jet printers programmed pulses of heat are applied to the composition in a reservoir by means of a resistor adjacent to the orifice, thereby causing the composition to be ejected in the form of small droplets directed towards the substrate during relative movement between the substrate and the orifice.
  • the oscillation of a small crystal causes ejection of the composition from the orifice.
  • the image is preferably text, a picture, a photorealistic image or a combination thereof.
  • the substrate is preferably paper, plastic, metal or glass, more preferably a treated substrate such as a coated paper or coated plastic, especially plain paper.
  • a treated substrate such as a coated paper or coated plastic, especially plain paper.
  • Preferred papers have an acid, alkaline or neutral character.
  • Examples of commercially available treated papers include HP Premium Coated Paper TM , HP Photopaper TM , HP Printing paper TM (available from Hewlett Packard Inc.); Stylus Pro 720 dpi Coated Paper TM , Epson Photo Quality Glossy Film TM , Epson Photo Quality Glossy Paper TM (all available from Seiko Epson Corp.); Canon HR 101 High Resolution Paper TM , Canon GP 201 Glossy Paper TM , Canon HG 101and HG201 High Gloss Film TM , Canon PR101 TM (all available from Canon); Kodak Premium Photopaper, Kodak Premium InkJetpaper TM (available from Kodak); Konica Inkjet Paper QP TM Professional Photo Glossy, Konica Inkjet Paper QP TM Professional Photo 2-sided Glossy, Konica Inkjet Paper QP TM Premium Photo Glossy, Konica Inkjet Paper QP TM Premium Photo Silky
  • any groups shown in the free acid form also include the salt form.
  • the formulae shown in this specification cover all tautomers thereof.
  • alkali metal salts especially lithium, sodium and potassium salts, ammonium and substituted ammonium salts and mixtures thereof.
  • Especially preferred salts are salts with ammonia and volatile amines.
  • the free acid form may be converted into a salt using known techniques.
  • an alkali metal salt may be converted into a salt with ammonia or an amine by dissolving an alkali metal salt of the composition in water, acidifying with a mineral acid and adjusting the pH of the solution to pH 9 to 9.5 with ammonia or the amine and removing the alkali metal cations by dialysis.
  • the preferred optionally substituted homocyclic or heterocyclic group groups represented by A are optionally substituted aryl, heteroaryl and non-aromatic cyclic groups.
  • Preferred optionally substituted aryl groups represented by A, L 1 and L 2 are each independently optionally substituted phenyl, biphenyl or naphthyl. In another embodiment of the present invention it is preferred that A is optionally substituted heteroaryl.
  • Preferred optionally substituted heteroaryl groups represented by A, L 1 and L 2 are any heterocycle or substituted heterocycle comprising a 5- to 7- membered ring.
  • preferred non-aromatic heterocyclic groups represented by A comprise a 5- to 7- membered ring, preferably comprising at least one double bond.
  • heteroaryl groups include pyridyl, furyl, thienyl, thiazolyl, isothiazolyl, imidazolyl, benzimidazolyl, pyrazinyl, pyrimidyl, quinolyl, isoquinolyl, benzofuryl, benzothienyl, pyrazolyl, indolyl, purinyl, isoxazolyl, oxazolyl, thiadiazolyl and furazanyl groups.
  • non-aromatic cyclic groups include pyridonyl, pyrazolonyl, piperidinyl, piperazinyl, pyrrolidinyl, morpholinyl, tetrahydrofuranyl, tetrahydrothiophenyl and tetrahydropyranyl, with pyridonyl being especially preferred.
  • Preferred optionally substituted alkenyl groups are of the Formula (2) and tautomers thereof: wherein:
  • Y 1 is alkyl it is preferably C 1-8 -alkyl, more preferably C 1-4 -alkyl.
  • Y 1 is aryl it is preferably phenyl.
  • X 1 is preferably OR, CO 2 R or NR in which R is as defined above.
  • Y is CO 2 R 1
  • Y 1 is OR 1
  • X 1 is OR 1 wherein each R 1 independently is H or C 1-4 -alkyl.
  • Optional substituents which may be present on A , L 1 and L 2 are preferably selected from OH, SO 3 H CN, carbonamido, PO 3 H 2 , CO 2 H NO 2 NH 2 , optionally substituted alkyl (especially C 1-4 -alkyl optionally carrying a sulpho, carboxy, phosphato, C 1-4 alkoxy, amino or hydroxy group), optionally substituted alkoxy (especially C 1-4 -alkoxy optionally carrying a sulpho, carboxy, phosphato, C 1-4 -alkoxy, C 1-4 -alkyl, amino or hydroxy group), optionally substituted aryl (especially phenyl or phenyl carrying from 1 to 3 substituents selected from sulpho, carboxy, phosphato, C 1-4 -alkoxy, amino, hydroxy and N carrying one or two C 1-4 -alkyl groups optionally carrying a sulpho, carboxy, phosphato, C 1-4 -alkoxy, amino or
  • A carries from 0 to 5 substituents, more preferably 1 to 4 substituents, especially 1, 2 or 3 substituents. In a preferred embodiment A is not 1,3-diaminophenyl.
  • optionally substituted phenyl and naphthyl groups represented by A there may be mentioned 2,4-dihydroxyphenyl, 3-sulfo-4,6-diaminophenyl, 2-hydroxy-4-diethylaminophenyl, 2-sulfo-4-diethylaminophenyl, 1-hydroxy-3,6-disulphonaphthyl and 1,8-dihydroxy-3,6-disulfonaphthyl.
  • Preferred optionally substituted heteroaryl groups represented by A are any heterocycle or substituted heterocycle comprising a 5- to 7-membered ring, more preferably optionally substituted pyridyl, pyrazolyl or 1,2,4-triazolyl.
  • L 1 and L 2 are each independently, or comprise, one or more arylene groups, more preferably one or two optionally substituted phenylene or naphthylene groups.
  • L 1 and L 2 are each independently optionally substituted phenylene or naphthylene, wherein at least one of L 1 and L 2 carries at least one substituent selected from sulpho, carboxy, C 1-4 -alkoxy and C 1-4 -alkoxy-OH.
  • L 1 and L 2 each independently carries from 0 to 3 substituents, more preferably 1 or 2 substituents, such that at least one of L 1 and L 2 carries at least one substituent selected from sulpho and carboxy. Further preferably at least one of L 1 and L 2 carries at least one substituent selected from C 1-4 -alkoxy and C 1-4 -alkoxy-OH
  • L 1 carries a substituent selected from sulpho and carboxy.
  • L 2 carries at least one substituent selected from sulpho, carboxy C 1-4 -alkoxy and C 1-4 -alkoxy-OH.
  • optionally substituted phenylene and naphthylene groups represented by L 1 and L 2 there may be mentioned 2-sulphophenylene, 2-carboxyphenylene, 2,5-dihydroxyethyloxyphenylene, 2,5-dimethoxyphenylene, 2,5-disulphophenylene, 2,5-diethoxyphenylene, 2-methyl-5-methoxyphenylene and 7-sulphonaphthylene.
  • Unmetallised dyes as described in the present invention are cheaper and easier to make than the corresponding metal chelates and they are more environmentally friendly due to the absence of, for example, transition metals.
  • the compound of Formula (1) is black.
  • the compound of Formula (1) is preferably of the Formula (1) wherein:
  • the compound of Formula (1) is of the Formula (1) wherein:
  • A is optionally substituted pyridonyl.
  • L 1 is phenyl or naphthyl optionally carrying a substituent selected from sulpho and carboxy.
  • L 2 is phenyl or naphthyl carrying at least one substituent selected from sulpho, carboxy, C 1-4 -alkoxy and C 1-4 -alkoxy-OH. More preferably L 2 is phenyl carrying two C 1-4 -alkoxy-OH substituents.
  • a preferred tris-azo compound,or a salt thereof, according to the second aspect of the invention is one wherein:
  • a more preferred tris-azo compound of Formula (1),or a salt thereof, according to the second aspect of the invention is one wherein:
  • composition comprising a tris-azo compound of Formula (1) or salt thereof as defined in relation to the first aspect of the present invention and a liquid medium comprising water and an organic solvent, wherein the compound of Formula (1) is not Formula (3) or a salt thereof:
  • the group represented by A in the compound of Formula (1) is not 1,3-diaminophenyl.
  • composition preferably comprises:
  • the process preferably uses the aforementioned composition.
  • the number of parts of component (a) is preferably from 0.1 to 20, more preferably from 0.5 to 15, and especially from 1 to 5 parts.
  • the number of parts of component (b) is preferably from 99.9 to 80, more preferably from 99.5 to 85, especially from 99 to 95 parts.
  • component (a) is completely dissolved in component (b).
  • component (a) has a solubility in component (b) at 20°C of at least 10%. This allows the preparation of liquid dye concentrates which may be used to prepare inks and reduces the chance of the dye precipitating if evaporation of the liquid medium occurs during storage.
  • the weight ratio of water to organic solvent is preferably from 99:1 to 1:99, more preferably from 99:1 to 50:50 and especially from 95:5 to 80:20.
  • the organic solvent present in the mixture of water and organic solvent is a water-miscible organic solvent or a mixture of such solvents.
  • Preferred water-miscible organic solvents include C 1-6 -alkanols, preferably methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, cyclopentanol and cyclohexanol; linear amides, preferably dimethylformamide or dimethylacetamide; ketones and ketone-alcohols, preferably acetone, methyl ether ketone, cyclohexanone and diacetone alcohol; water-miscible ethers, preferably tetrahydrofuran and dioxane; diols, preferably diols having from 2 to 12 carbon atoms, for example pentane-1,5-diol, ethylene
  • Especially preferred water-soluble organic solvents are cyclic amides, especially 2-pyrrolidone, N-methyl-pyrrolidone and N-ethyl-pyrrolidone; diols, especially 1,5-pentane diol, ethyleneglycol, thiodiglycol, diethyleneglycol and triethyleneglycol; and mono- C 1-4 -alkyl and C 1-4 -alkyl ethers of diols, more preferably mono- C 1-4 -alkyl ethers of diols having 2 to 12 carbon atoms, especially ((2-methoxy-2)-ethoxy)-2-ethoxyethanol.
  • diols especially 1,5-pentane diol, ethyleneglycol, thiodiglycol, diethyleneglycol and triethyleneglycol
  • mono- C 1-4 -alkyl and C 1-4 -alkyl ethers of diols more preferably mono- C 1-4 -alkyl ether
  • the liquid medium comprises an oxidant.
  • Preferred low melting point solids have a melting point in the range from 60°C to 125°C.
  • Suitable low melting point solids include long chain fatty acids or alcohols, preferably those with C 18-24 chains, and sulphonamides.
  • the compound of Formula (1) may be dissolved in the low melting point solid or may be finely dispersed in it.
  • the liquid medium will further comprise one or more surfactants, for example anionic and/or nonionic surfactants.
  • anionic surfactants include: Sulfonate surfactants such as Sulfosuccinates (Aerosol TM OT, A196; AY and GP, available from CYTEC) and Sulfonates (Aerosol TM DPOS-45, OS available from CYTEC; Witconate TM C-50H available from WITCO; Dowfax TM 8390 available from DOW); and Fluoro surfactants (Fluorad TM FC99C available from 3M).
  • Sulfonate surfactants such as Sulfosuccinates (Aerosol TM OT, A196; AY and GP, available from CYTEC) and Sulfonates (Aerosol TM DPOS-45, OS available from CYTEC; Witconate TM C-50H available from WITCO; Dowfax TM 8390 available from DOW
  • nonionic surfactants include: Fluoro surfactants (Fluorad TM FC170C available from 3M); Alkoxylate surfactants (Tergitol TM series 15S-5, 15S-7, and 15S-9 available from Union Carbide); and Organosilicone surfactants (Silwet TM L-77 and L-76-9 available from WITCO).
  • the buffers may optionally be included in the liquid medium to modulate pH of the ink.
  • the buffers can be organic-based biological buffers or inorganic buffers, preferably, organic-based.
  • examples of preferably-employed buffers include tris(hydroxymethyl)aminomethane (TRIS), available from companies such as Aldrich Chemical (Milwaukee, Wis.), 4-morpholine ethanesulfonic acid (MES), 4-morpholinepropanesulfonic acid (MOPS), and beta-hydroxy-4-morpholinepropanesulfonic acid (MOPSO).
  • TAS tris(hydroxymethyl)aminomethane
  • MES 4-morpholine ethanesulfonic acid
  • MOPS 4-morpholinepropanesulfonic acid
  • MOPSO beta-hydroxy-4-morpholinepropanesulfonic acid
  • the buffers employed should provide a pH ranging from about 3 to about 9 in the practice of the invention, preferably about 4 to about 6 and most preferably from about 4
  • One or more of the biocides commonly employed in inkjet inks may optionally be used in the ink, such as Nuosept TM 95, available from Huls America (Piscataway, N.J.); Proxel TM GXL, available from Zeneca (Wilmington, Del.); and glutaraldehyde, available from Union Carbide Company (Bound Brook, N.J.) under the trade designation Ucarcide 250.
  • Nuosept TM 95 available from Huls America (Piscataway, N.J.)
  • Proxel TM GXL available from Zeneca (Wilmington, Del.)
  • glutaraldehyde available from Union Carbide Company (Bound Brook, N.J.) under the trade designation Ucarcide 250.
  • Inks according to the invention may optionally also include one or more metal chelator.
  • metal chelators are used to bind transition metal cations that may be present in the ink.
  • Examples of preferred metal chelators include: ethylenediaminetetraacetic acid (“EDTA”), diethylenediaminepentaacetic acid (“DPTA”), trans-1,2-diaminocyclohexanetetraacetic acid (“CDTA”), ethylenedinitrilotetraacetic acid (“EGTA”), or other chelators.
  • inks according to the invention have a pH of from about 3 to about 5, preferably from about 3.5 to about 4.5.
  • the pH of the composition is preferably from 4 to 11, more preferably from 7 to 10.
  • the composition comprises a buffer.
  • the viscosity of the composition at 25°C is preferably less than 50cP, more preferably less than 20 cP and especially less than 5cP.
  • the composition preferably has a concentration of less than 500 parts per million, more preferably less than 100 parts per million of halide ions. It is especially preferred that the composition has less than 100, more preferably less than 50 parts per million of divalent and trivalent metals, wherein parts refer to parts by weight relative to the total weight of the composition.
  • purifying the compositions to reduce the concentration of these undesirable ions reduces nozzle blockage in ink jet printing heads, particularly in thermal ink jet printers. Similarly low levels as divalent and trivalent metals are also preferred.
  • the compounds of the invention may be used as the sole colorant in the compositions because of their attractive black shade. However, if desired, one may combine the present compounds together and/or with one or more further colorants to reduce nozzle blockage (by improving their solubility) or if a slightly different shade is required for a particular end use.
  • the further colorants are preferably dyes. When further colorants are included in the composition these are preferably selected from black, magenta, cyan and yellow colorants and combinations thereof.
  • Suitable further black colorants include C.I.Food Black 2, C.I.Direct Black 19, C.I.Reactive Black 31, PRO-JET TM Fast Black 2, C.I.Direct Black 195; C.I.Direct Black 168; and black dyes described in patents by Lexmark (e.g. EP 0 539,178 A2 , Example 1, 2, 3, 4 and 5), Orient Chemicals (e.g. EP 0 347 803 A2 , pages 5-6, azo dyes 3, 4, 5, 6, 7, 8, 12, 13, 14, 15 and 16) and Seiko Epson Corporation.
  • Suitable further magenta colorants include PRO-JET TM Fast Magenta 2 .
  • Suitable further yellow colorants include C.I.Direct Yellow 142; C.I.Direct Yellow 132; C.I.Direct Yellow 86; PRO-JET TM Yellow OAM; PRO-JET TM Fast Yellow 2; C.I.Direct Yellow 85; C.I. Direct Yellow 173; and C.I.Acid Yellow 23.
  • Suitable further cyan colorants include phthalocyanine colorants, C.I. Direct Blue 199 and C.I. Acid Blue 99.
  • composition may also contain additional components conventionally used in ink jet printing inks, for example viscosity and surface tension modifiers, corrosion inhibitors, biocides, kogation reducing additives and surfactants which may be ionic or non-ionic.
  • additional components conventionally used in ink jet printing inks, for example viscosity and surface tension modifiers, corrosion inhibitors, biocides, kogation reducing additives and surfactants which may be ionic or non-ionic.
  • the diazotisations are carried out using a diazotising agent, especially sodium nitrite under acidic conditions. Further preferably the diazotisations are carried out at a temperature of 0 to 5°C.
  • a diazotising agent especially sodium nitrite under acidic conditions.
  • the diazotisations are carried out at a temperature of 0 to 5°C.
  • a further aspect of the present invention provides a paper, an overhead projector slide or a textile material printed with a composition, a compound or by means of a process according to the present invention.
  • a still further aspect of the present invention provides an ink jet printer cartridge, optionally refillable, comprising one or more chambers and a composition, wherein the composition is present in at least one of the chambers and the composition is as defined in the third aspect of the present invention.
  • the present compounds and compositions provide prints of attractive, neutral black shades that are particularly well suited for the ink jet printing of text and images.
  • the compositions have good storage stability and low tendency to block the very fine nozzles used in ink jet printers. Furthermore, the resultant images have good optical density, light-fastness, wet-fastness and resistance to fading in the presence of oxidising air pollutants (e.g. ozone).
  • oxidising air pollutants e.g. ozone
  • step 1 The product of step 1 (211.5g) was dissolved in acetic acid (1800ml). A mixture of nitric acid (51.9ml) and acetic acid (200ml) was then added over 20 minutes keeping the temperature below 20°C. After stirring at room temperature overnight the solution was drowned into water (91) and the product isolated by filtration, washed with water and recrystallised from ethanol to give 209g of product.
  • the monoazo product from Stage one (24.75g; 0.05mol) was dissolved in water (300ml) with stirring at pH 10 to which sodium nitrite (6.90g; 0.1 mol) and acetone (200ml) were added.
  • the resulting mixture was then added to 0.10M hydrochloric acid (70ml) with stirring at room temperature. After stirring for 1 h, the excess nitrous acid was destroyed by the addition of sulphamic acid.
  • the resulting diazonium salt was then added to a stirred solution of chromotropic acid (20.00g; 0.05mol) at 0 - 10°C at pH 7- 8 maintained by the addition of 2N lithium hydroxide when necessary.
  • the amino disazo compound from Stage Two (12.00g; 0.0158mol) was dissolved in water (250ml) with stirring at pH 9 to which calsolene oil (1ml) and sodium nitrite (1.20g; 0.0174 mol) was added. The resulting solution was then added to ice / water (100g) containing concentrated hydrochloric acid (5ml) with stirring at 0 -10°C. After stirring for 1 h at 0-10°C the excess nitrous acid was destroyed by the addition of sulphamic acid.
  • the resulting diazonium salt was added to a stirred solution of 1-(4-sulphophenyl)-3-carboxy-5-pyrazolone (5.39g; 0.19mol) in water (100ml) at 0 - 10°C and then adjusted to pH 7. After stirring overnight the solution was poured into acetone (3l) with stirring, filtered and washed with acetone. The solid dissolved in water and dialysed to low conductivity to give after evaporation (80°C) a black powder (11.61g; 68.8%; ⁇ max 612nm and an ⁇ max of 82232; mass spectrum (M-H)-ve 1037).
  • Example 1 The method of Example 1 was repeated except that in place of 4-amino-3-sulpho acetanilide there was used 4-amino-3-carboxyacetanilide.
  • the resultant compound had a ⁇ max at 602nm and an ⁇ max of 79,227.
  • Example 2 The method of Example 2 was repeated except that in place of 2,5-di-(2-acetoxyethoxy)aniline there was used 2,5-di-(methoxy)aniline.
  • the resultant compound had a ⁇ max at 601 nm.
  • Example 1 The method of Example 1 was repeated except that in place of 2,5-di-(2-acetoxyethoxy)aniline there was used 1-amino-7-sulphonaphthalene.
  • the resultant compound had a ⁇ max at 604 nm and an ⁇ max of 69,419.
  • Examples 5 to 38 shown in Table 1 were prepared by following the general method of Example 1, except that (with reference to Table 1) in place of 1-(4-sulphophenyl)-3-carboxy-5-pyrazolone there was used the compound shown in Column A, in place of 4-amino-3-sulphoacetanilide there was used the compound shown in Column L 1 and in place of 2,5-di-(2-acetoxyethoxy)aniline there was used the compound shown in column L 2 unless otherwise indicated (“N/A”) in each case.
  • the final dye structure is shown for each example in Table 1.
  • stage 2 The product from stage 2 (0.01 mol) was dissolved in water (150ml) at pH 9,sodium nitrite ( 0.77g: 0.011mol) added. The resulting suspension was added to ice / water (100g) containing concentrated hydrochloric acid (6ml) at 0 - 10°C. After stirring for 2 hours the excess nitrous acid was destroyed by the addition of sulphamic acid.
  • the resulting diazonium salt was added to a stirred solution of 1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carboxamide (2.45g; 0.0125 mol) in water (25ml) at 0 -10°C and pH 9 - 10 maintained by the addition of 2N lithium hydroxide when necessary. After stirring overnight the product was precipitated by the addition of acetone then filtered and washed to give after drying a black solid (1.01g;10%; ⁇ max 598nm, 631 nm (M-3H) -ve 324).
  • Examples 40 to 44 shown in Table 2 were prepared by following the general method of Example 39, except that (with reference to Table 2) in place of 1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carboxamide there was used the compound shown in Column A, in place of gamma acid there was used the amine shown in Column L 1 and in place of 4-amino-3-sulpho acetanilide there was used the amine shown in column L 2 .
  • the final dye structure is shown for each example in Table 2.
  • Table 2 Ex A L 1 L 2 Final dye structure ⁇ max ⁇ max (nm) 40 83444 611 41 77567 655 42 85240 666 43 576 44 582
  • Example 1 4-Amino-3-sulpho acetanilide diazonium salt (0.1 mol) prepared as Example 1 (stage 1) was added to a stirred solution of 1-hydroxy-6-amino-3,5-naphthalenedisulphonic acid (35.09g; 0.11 mol) at 0-10°C and pH 9-10 maintained by the addition of 2N lithium hydroxide when necessary. After stirring overnight the solution was adjusted to pH8, the product was precipitated by the addition of 30% (w/v) lithium chloride, then filtered and washed with 40% (w/v) lithium chloride solution. The resulting solid was dissolved in water at pH10 to give 688.7g of a solution of 0.085 mol of the mono-azo intermediate above.
  • Lithium hydroxide hydrate (50g; 1.24mol) was added to 1000 ml of the stirred solution from stage 2 (0.073 mol), which was then heated at 70-80°C for 2.5 hours. The solution was adjusted to pH 9 with concentrated hydrochloric acid and then cooled overnight to give 1279.0g of a solution containing 0.072 mol of the dis-azo intermediate above.
  • Example Compound (parts) Compound (parts) 46 Example 8 (1) Example 1 (0.9) 47
  • Example 4 (1) C.I. Direct Yellow 132 (0.1) 48
  • Example 8 (1)
  • Example 13 (0.5) 49
  • Example 15 (1)
  • Example 14 (1)
  • Example 8 (1)
  • Example 1 (1)
  • Example 8 (1) 52
  • Example 12 (1)
  • Inks may be prepared according to the following formulation wherein Dye is the compound or mixture from each of the above Examples above: 2-Pyrrolidone 5 parts Thiodiglycol 5 parts SurfynolTM 465 1 part (from Air Products Inc., USA) Dye 3 parts Water 86 parts
  • inks described in Tables 4 and 5 may be prepared wherein the Dye described in the first column is the compound or mixture made in the above Example of the same number. Numbers quoted in the second column onwards refer to the number of parts of the relevant ingredient and all parts are by weight.
  • the inks may be applied to paper by thermal or piezo ink jet printing.
  • Example 60 The inks described in the first paragraph of Example 60 were ink-jet printed onto a variety of papers using a Hewlett Packard DeskJet 560CTM.
  • the CIE colour co-ordinates of each print (a, b, L, Chroma and hue H) were measured using a Gretag Spectrolino SpectrodensitometerTM with 0°/45° measuring geometry with a spectral range of 400-700nm at 20nm spectral intervals, using illuminant D50 with a 2° (CIE 1931) observer angle and a density operation of status A. No less than 2 measurements were taken diagonally across a solid colour block on the print with a size greater than 10mm x 10mm.
  • Table 6 The properties of the resultant prints are shown in Table 6, where the example number of the dye used to prepare the ink is indicated in the left hand column, and ROD is Relative Optical Density.
  • the inks from Examples 61 to 66 were printed onto the substrate shown using a HP560 TM ink jet printer.
  • the printed substrate was then assessed for ozone stability using an ozone test cabinet from Hampden Test Equipment. The test was carried out for 24 hours at 40°C and 50% relative humidity in the presence of 1 part per million of ozone.
  • Fastness of the printed ink to ozone was judged by the difference in the optical density before and after exposure to ozone using a Gretag Spectrolino Spectrodensitometer. Thus, the lower the %OD loss the greater the ozone fastness.
  • Table 8 where the example number of the dye used to prepare the ink is indicated in the left hand column.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP03811422A 2002-11-15 2003-11-13 Trisazo dyes for inks for ink jet printing Expired - Lifetime EP1563012B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB0226708.6A GB0226708D0 (en) 2002-11-15 2002-11-15 Compounds
GB0226708 2002-11-15
PCT/GB2003/004928 WO2004046252A1 (en) 2002-11-15 2003-11-13 Trisazo dyes for inks for ink jet printing

Publications (2)

Publication Number Publication Date
EP1563012A1 EP1563012A1 (en) 2005-08-17
EP1563012B1 true EP1563012B1 (en) 2011-07-27

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EP03811422A Expired - Lifetime EP1563012B1 (en) 2002-11-15 2003-11-13 Trisazo dyes for inks for ink jet printing

Country Status (12)

Country Link
US (1) US7530685B2 (ko)
EP (1) EP1563012B1 (ko)
JP (1) JP4634805B2 (ko)
KR (1) KR101023261B1 (ko)
CN (1) CN1738868B (ko)
AT (1) ATE517950T1 (ko)
AU (1) AU2003302025A1 (ko)
GB (1) GB0226708D0 (ko)
HK (1) HK1088920A1 (ko)
MX (1) MXPA05005026A (ko)
TW (1) TWI329664B (ko)
WO (1) WO2004046252A1 (ko)

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CN101068886A (zh) * 2004-12-03 2007-11-07 佳能株式会社 偶氮颜料分散液的制备方法
JP4876549B2 (ja) * 2004-12-16 2012-02-15 三菱化学株式会社 アゾ色素、これを用いた異方性色素膜用組成物、異方性色素膜および偏光素子
US7247195B2 (en) * 2005-03-09 2007-07-24 Hewlett-Packard Development Company, L.P. Dye sets for ink-jet ink imaging
MX2008013465A (es) * 2006-05-09 2008-10-30 Fujifilm Imaging Colorants Ltd Colorantes trisazo, composiciones y procesos de impresion por inyeccion de tinta.
GB0609091D0 (en) * 2006-05-09 2006-06-21 Fujifilm Imaging Colorants Ltd Azo compounds, compositions and ink jet printing processes
JP2008056898A (ja) * 2006-06-15 2008-03-13 Mitsubishi Chemicals Corp 異方性色素膜用アゾ色素
GB0620774D0 (en) * 2006-10-19 2006-11-29 Fujifilm Imaging Colorants Ltd Improvements in and relating to azo compounds and their use in printing
WO2008096697A1 (ja) * 2007-02-05 2008-08-14 Nippon Kayaku Kabushiki Kaisha トリスアゾ化合物、インク組成物、プリント方法及び着色体
JP2009013293A (ja) * 2007-07-04 2009-01-22 Sumitomo Chemical Co Ltd アゾ化合物又はその塩
EP2220168B1 (en) * 2007-11-30 2012-07-25 Hewlett-Packard Development Company, L.P. Black ink-jet inks with reduced lightness and haze
GB0802874D0 (en) * 2008-02-16 2008-03-26 Fujifilm Imaging Colorants Ltd Improvements in and relating to polyazo compounds containing heterocyclic aromatic groups and their use in ink jet printing
JP2013504647A (ja) * 2009-09-11 2013-02-07 フジフィルム・イメイジング・カラランツ・リミテッド 染料およびインクジェット印刷におけるそれらの使用
JP5866150B2 (ja) 2010-07-30 2016-02-17 富士フイルム株式会社 新規なアゾ化合物、水溶液、インク組成物、インクジェット記録用インク、インクジェット記録方法、インクジェット記録用インクカートリッジ、及びインクジェット記録物
JP5785799B2 (ja) 2010-07-30 2015-09-30 富士フイルム株式会社 新規なアゾ化合物、水溶液、インク組成物、インクジェット記録用インク、インクジェット記録方法、インクジェット記録用インクカートリッジ、及びインクジェット記録物
JP2014198816A (ja) 2012-09-26 2014-10-23 富士フイルム株式会社 アゾ化合物、水溶液、インク組成物、インクジェット記録用インク、インクジェット記録方法、インクジェット記録用インクカートリッジ、及びインクジェット記録物
JP7054657B2 (ja) * 2018-07-24 2022-04-14 日本化薬株式会社 アゾ化合物、インク組成物、記録方法及び着色体

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Also Published As

Publication number Publication date
KR20050086644A (ko) 2005-08-30
HK1088920A1 (en) 2006-11-17
CN1738868A (zh) 2006-02-22
TWI329664B (en) 2010-09-01
TW200424268A (en) 2004-11-16
JP4634805B2 (ja) 2011-02-16
KR101023261B1 (ko) 2011-03-21
JP2006506499A (ja) 2006-02-23
WO2004046252A1 (en) 2004-06-03
EP1563012A1 (en) 2005-08-17
GB0226708D0 (en) 2002-12-24
AU2003302025A1 (en) 2004-06-15
CN1738868B (zh) 2010-07-14
US20060054054A1 (en) 2006-03-16
ATE517950T1 (de) 2011-08-15
MXPA05005026A (es) 2005-08-03
US7530685B2 (en) 2009-05-12

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